Method and apparatus for extracting carbon dioxide from air

ABSTRACT

A method and apparatus for extracting CO 2  from air comprising an anion exchange material formed in a matrix exposed to a flow of the air, and for delivering that extracted CO 2  to controlled environments. The present invention contemplates the extraction of CO2 from air using conventional extraction methods or by using one of the extraction methods disclosed; e.g., humidity swing or electro dialysis. The present invention also provides delivery of the CO 2  to greenhouses where increased levels of CO 2  will improve conditions for growth. Alternatively, the CO 2  is fed to an algae culture.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority from U.S. ProvisionalApplication Ser. No. 60/827,849, filed Oct. 2, 2006, and 60/829,376,filed Oct. 13, 2006, the contents of which are incorporated herein byreference.

FIELD OF THE INVENTION

The present invention in one aspect relates to removal of selected gasesfrom air. The invention has particular utility for the extraction andsequestration of carbon dioxide (CO₂) from air and will be described inconnection with such utilities, although other utilities arecontemplated.

BACKGROUND OF THE INVENTION

There is compelling evidence to suggest that there is a strongcorrelation between the sharply increasing levels of atmospheric CO₂with a commensurate increase in global surface temperatures. This effectis commonly known as Global Warming. Of the various sources of the CO₂emissions, there are a vast number of small, widely distributed emittersthat are impractical to mitigate at the source. Additionally, largescale emitters such as hydrocarbon-fueled power plants are not fullyprotected from exhausting CO₂ into the atmosphere. Combined, these majorsources, as well as others, have lead to the creation of a sharplyincreasing rate of atmospheric CO₂ concentration. Until all emitters arecorrected at their source, other technologies are required to capturethe increasing, albeit relatively low, background levels of atmosphericCO₂. Efforts are underway to augment existing emissions reducingtechnologies as well as the development of new and novel techniques forthe direct capture of ambient CO₂. These efforts require methodologiesto manage the resulting concentrated waste streams of CO₂ in such amanner as to prevent its reintroduction to the atmosphere.

The production of CO, occurs in a variety of industrial applicationssuch as the generation of electricity power plants from coal and in theuse of hydrocarbons that are typically the main components of fuels thatare combusted in combustion devices, such as engines. Exhaust gasdischarged from such combustion devices contains CO₂ gas, which atpresent is simply released to the atmosphere. However, as greenhouse gasconcerns mount, CO₂ emissions from all sources will have to becurtailed. For mobile sources the best option is likely to be thecollection of CO₂ directly from the air rather than from the mobilecombustion device in a car or an airplane. The advantage of removing CO₂from air is that it eliminates the need for storing CO₂ on the mobiledevice.

Extracting carbon dioxide (CO₂) from ambient air would make it possibleto use carbon-based fuels and deal with the associated greenhouse gasemissions after the fact. Since CO₂ is neither poisonous nor harmful inparts per million quantities, but creates environmental problems simplyby accumulating in the atmosphere, it is possible to remove CO₂ from airin order to compensate for equally sized emissions elsewhere and atdifferent times.

Most prior art methods, however, result in the inefficient capture ofCO₂ from air because these processes heat or cool the air, or change thepressure of the air by substantial amounts. As a result, the net loss inCO₂ is negligible as the cleaning process may introduce CO₂ into theatmosphere as a byproduct of the generation of electricity used to powerthe process.

Various methods and apparatus have been developed for removing CO₂ fromair. For example, we have recently disclosed methods for efficientlyextracting carbon dioxide (CO₂) from ambient air using capture solventsthat either physically or chemically bind and remove CO₂ from the air. Aclass of practical CO₂ capture sorbents include strongly alkalinehydroxide solutions such as, for example, sodium or potassium hydroxide,or a carbonate solution such as, for example, sodium or potassiumcarbonate brine. See for example published PCT ApplicationPCT/US05/29979 and PCT/US06/029238.

There are also many uses for sequestered CO₂. This includes the use ofCO₂ in greenhouses where higher levels of CO₂ contribute to increasedplant growth. CO₂ may also be supplied to algae cultures. Researchershave shown that algae can remove up to 90% of gaseous CO₂ from airstreams enriched in CO₂ and can also reduce the CO₂ concentration inambient air.

SUMMARY OF THE INVENTION

The present invention provides a system, i.e. a method and apparatus forextracting carbon dioxide (CO₂) from ambient air and for delivering thatextracted CO₂ to controlled environments.

In a first exemplary embodiment, the present invention extracts CO₂ fromambient air and delivers the extracted CO₂ to a greenhouse. Preferably,the CO₂ is extracted from ambient air using a strong base ion exchangeresin that has a strong humidity function, that is to say, an ionexchange resin having the ability to take up CO₂ as humidity isdecreased, and give up CO₂ as humidity is increased. Several aspects ofthis invention can also be used to transfer CO₂ from the collectormedium into the air space of a greenhouse where the CO₂ is again fixedin biomass. In a preferred embodiment of the invention, CO₂ is extractedfrom ambient air using an extractor located adjacent to a greenhouse,and the extracted CO₂ is delivered directly to the interior of thegreenhouse for enriching the greenhouse air with CO₂ in order to promoteplant growth.

In a second exemplary embodiment, this invention allows the transfer ofCO₂ from a collector medium into an algae culture, where the CO₂ carbonis fixed in biomass. The algae biomass can then be used for theproduction of biochemical compounds, fertilizer, soil conditioner,health food, and biofuels to name just a few applications or end-uses.

This invention also discloses transfer of CO₂ in gaseous phase and as abicarbonate ion. In one embodiment, a calcareous algae is used whichcreates calcium carbonate CaCO₃ internally, and precipitates the CaCO₃out as limestone.

Accordingly, in broad concept, the present invention extracts CO₂ fromambient air using one of several CO₂ extraction techniques as described,for example, in our aforesaid PCT/US05/29979 and PCT/US06/029238. Wherea carbonate/bicarbonate solution is employed as the primary CO₂ sorbent,the CO₂ bearing sorbent may be used directly as a feed to the algae.Where the CO₂ is extracted using an ion exchange resin as taught, forexample in our aforesaid PCT/US06/029238 application, the CO₂ isstripped from the resin using a secondary carbonate/bicarbonate washwhich then is employed as a feed to the algae. In a preferredalternative embodiment, the carbonate is fed to the algae in a lightenhanced bioreactor.

Thus, the present invention provides a simple, relative low-costsolution that addresses both CO₂ capture from ambient air and subsequentdisposal of the captured CO₂.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and advantages of the present invention will be seenfrom the following detailed description, taken in conjunction with theaccompanying drawings, wherein

FIG. 1 is a block flow diagram illustrating the use of humiditysensitive ion exchange resins in accordance with the present invention;

FIGS. 2 a and 2 b are schematic views of a CO₂ extractor/greenhousefeeder in accordance with the present invention, where filter units arelocated adjacent an exterior wall;

FIGS. 3 a and 3 b are schematic views of a CO₂ extractor/greenhousefeeder in accordance with the present invention, where filter units arelocated adjacent to the roof of the greenhouse;

FIG. 4 is a schematic view of a CO₂ extractor/greenhouse feeder showingan arrangement of filter units according the present invention;

FIG. 5 is a schematic view of a CO₂ extractor/greenhouse feeder showingfilter units arranged on a track according to an alternative embodimentof the present invention;

FIG. 6 is a schematic view of a CO₂ extractor/greenhouse feederincluding convection towers according to an alternative embodiment ofthe present invention;

FIG. 7 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention utilizing a humidity swing applied toa collector medium;

FIG. 8 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention utilizing a humidity swing applied toa collector solution;

FIG. 9 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention transferring gaseous CO₂ by anelectro-dialysis process;

FIG. 10 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention transferring bicarbonate by anelectro-dialysis process;

FIG. 11 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention utilizing an algae culture forcollector regeneration;

FIG. 12 is a schematic view of a CO₂ extractor and algae culture similarto FIG. 11 utilizing a nutrient solution;

FIG. 13 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention utilizing a gas-permeable membrane;

FIG. 14 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention utilizing an anion-permeablemembrane;

FIG. 15 is a schematic view of a CO₂ extractor and algae culture similarto FIG. 14;

FIG. 16 is a schematic view of a CO₂ extractor and algae cultureaccording to the present invention including a shower; and

FIG. 17 is a schematic view of a CO₂ extractor and algae culture similarto FIG. 16.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In broad concept, the present invention in one aspect extracts carbondioxide from ambient air using a conventional CO₂ extraction method orone of the improved CO₂ extraction methods disclosed in our aforesaidPCT Applications, or disclosed herein, and releases at least a portionof the extracted CO₂ to a closed environment.

In a first exemplary embodiment, this closed environment is agreenhouse. Preferably, but not necessarily, the CO₂ extractor islocated adjacent to the greenhouse and, in a preferred embodiment theextractor also provides shading for crops grown in greenhouses which aresensitive to strong sunlight, and/or reduces cooling requirements forthe greenhouse.

In one approach to CO₂ capture, the resin medium is regenerated bycontact with the warm highly humid air. It has been shown that thehumidity stimulates the release of CO₂ stored on the storage medium andthat CO₂ concentrations between 3% and 10% can be reached by thismethod, and in the case of an evacuated/dehydrated system, close to 100%can be reached. In this approach the CO₂ is returned to gaseous phaseand no liquid media are brought in contact with the collector material.

The CO₂ extractor is immediately adjacent to the greenhouse and is movedoutside the greenhouse to collect CO₂ and moved into the greenhouse togive off CO₂. In such embodiment, the CO₂ extractor preferably comprisesa humidity sensitive ion exchange resin in which the ion exchange resinextracts CO₂ when dry, and gives the CO₂ up when exposed to higherhumidity. A humidity swing may be best suited for use in arid climates.In such environment the extractor is exposed to the hot dry air exteriorto the greenhouse, wherein CO₂ is extracted from the air. The extractoris then moved into the warm, humid environment of the greenhouse wherethe ion exchange resin gives up CO₂. The entire process may beaccomplished without any direct energy input other than the energy tomove the extractor from outside to inside the greenhouse and vice versa.

Ion exchange resins are commercially available and are used, forexample, for water softening and purification. We have found thatcertain commercially available ion exchange resins which are humiditysensitive ion exchange resins and comprise strong base resins,advantageously may be used to extract CO₂ from the air in accordancewith the present invention. With such materials, the lower the humidity,the higher the equilibrium carbon loading on the resin.

Thus, a resin which at high humidity level appears to be loaded with CO₂and is in equilibrium with a particular partial pressure of CO₂ willexhale CO₂ if the humidity is increased and absorb additional CO₂ if thehumidity is decreased. The effect is large, and can easily change theequilibrium partial pressure by several hundred and even severalthousand ppm. The additional take up or loss of carbon on the resin isalso substantial if compared to its total uptake capacity.

There also seems to be an effect on humidity on the transfercoefficient, i.e. the reaction kinetics seem to change with changinghumidity. However, the measured flux in and out of the resin seems todepend strongly on the difference between the actual partial pressureand the thermodynamic equilibrium pressure. As the equilibrium pressurechanges with humidity, the size of the flux can be affected without anactual change in the reaction kinetics.

In addition, it is possible that kinetics is affected by other issues.For example, ion exchange materials which we have found to beparticularly useful, are Anion 1-200 ion exchange membrane materialsavailable from Snowpure LLC, of San Clemente, Calif. The manufacturerdescribes Anion 1-200 ion exchange membrane material as a strong base,Type 1 functionality ion exchange material. This material, which isbelieved made according to the U.S. Pat. No. 6,503,957 and is believedto comprise small resin charts encapsulated—or partially encapsulated—inan inactive polymer like polypropylene. We have found that if one firsthydrates this material and then dries it, the material becomes porousand readily lets air pass through. The hydration/dehydration preparationis believed to act primarily to swell the polypropylene binder, and haslittle or no permanent effect on the resin, while the subsequenthumidity swings have no observed impact on the polypropylene binder. Wehave found that these strong base ion exchange resin materials have theability to extract CO₂ from dry air, and give the CO₂ out when humidityis raised without any other intervention. The ability of these materialsto extract CO₂ directly from the air, when dry, and exhale the CO₂ ashumidity is raised, has not previously been reported.

As noted supra, it is necessary to first hydrate this material and thendry it, before using, whereupon the material becomes porous and readilylets air pass through. Before hydration, the membrane material issubstantially non-porous, or at least it is unable to permit passage ofan appreciable amount of air through the membrane. However, afterhydration and drying, the material is believed to undergo irreversibledeformation of the polypropylene matrix during the resin swelling underhydration. Once the material has been deformed, the polypropylene matrixmaintains its extended shape even after the resin particles shrink whendrying. Thus, for substantially non-porous materials such as theSnowpure Ion Exchange material above described, it is necessary toprecondition the material by hydrating and then drying the materialbefore use.

We have observed a large change in the equilibrium partial pressure ofCO₂ over the resin with a change in humidity. Humidity either changesthe state of the resin, or alternatively the entire system that needs tobe considered is the CO₂/H₂O resin system. While not wishing to be boundby theory, it is believed that the free energy of binding CO₂ to theresin is a function of the H₂O partial pressure with which the resin isin equilibrium.

This makes it possible to have resins absorb or exhale CO₂ with a simpleswing in humidity without the need to resort to thermal swing and/orpressure swing, which would add to energy costs which could have anunfavorable effect with regard to the overall carbon dioxide balance ofthe system.

The amount of water involved in such a swing appears to be quite small.The possibility of a humidity swing also allows us to recover CO₂ froman air collector with minimal water losses involved.

Other strong base Type 1 and Type 2 functionality ion exchange materialsare available commercially from a variety of venders including Dow,DuPont and Rohm and Haas, and also advantageously may be employed in thepresent invention, either as available from the manufacturer, or formedinto heterogeneous ion-exchange membranes following, for example, theteachings of U.S. Pat. No. 6,503,957.

FIG. 1 illustrates a first embodiment of our invention. A primary ionexchange filter material 4 is provided in a recirculation cycle. Aprimary pump 1 or a secondary pump (not shown) is used to remove thebulk of the air in the system while valve V₁ is open and push it outthrough the air exhaust 2. At this point valve V₁ is closed and asecondary ion exchange capture resin is switched into the system byopening valves V₂ and V₃. The secondary ion exchange resin can beutilized to provide humidity and possibly some heat. Warm steamstimulates the release of CO₂ from the primary ion exchange filtermaterial 4, which is then captured on the secondary ion exchange resinwhich is still out of equilibrium with the CO₂ partial pressure. Thevolume of water in the system remains small as it is recirculated andnot taken up by the secondary resin. While CO₂ is unloading from theprimary ion exchange resin material 14 and being absorbed by thesecondary ion exchange resin, the bulk of the water cycles through theapparatus. The amount of water that can be devolved or absorbed is muchsmaller than the amount of CO₂ that is transferred. At the end of thecycle the primary ion exchange filter material 14 is refreshed and thesecondary ion exchange capture resin is loaded with CO₂.

This system could be used to transfer CO₂ from the air capture medium,e.g. an ion exchange resin onto a secondary resin without washing orwetting the primary resin. This has two advantages. First, the primaryresin is not directly exposed to chemicals such as amines that were usedin the past and described in our aforesaid PCT ApplicationPCT/US061/029,238. Second, we have seen that wet resins are ineffectivein absorbing CO₂ until they have dried out. It is therefore advantageousto avoid the wetting of the material and thus operate in this fashionwhere the resin is washed with low-pressure steam. Steam pressures couldbe less than 100 Pa and thus be saturated at temperatures similar toambient values. However, the CO₂ exchange is obviously accelerated athigher temperatures and higher steam pressures. The disadvantage ofraising temperatures would be additional energy consumption.

The design outlined here is a special example of a broader class ofdesigns where the secondary resin is replaced with any other sorbentmaterial that is capable of absorbing CO₂ without absorbing water. Suchsorbents may include liquid amines, ionic liquids, solid CO₂ sorbentssuch as lithium zirconate, lithium silicate, magnesium hydroxide orcalcium hydroxide, or any of a wide class of chemical or physicalsorbents capable of absorbing CO₂ from a gas mixture including watervapor and CO₂. The central concept is that of using a humidity swing,rather than a pressure or temperature swing to remove CO₂ from theprimary sorbent without bringing it in direct physical contact with asecondary sorbent.

Application in a Greenhouse for Improving Crop Yields

As noted supra, crop yield in greenhouses can be improved by increasingthe carbon dioxide level in the greenhouse air. The present inventionprovides for the introduction of carbon dioxide into a greenhousewithout combusting fuels emitting fossil fuel CO₂ into the air. Moreparticularly, we have found that we can employ humidity sensitive ionexchange resins to capture CO₂ from dry outside air, and then releasethe CO₂ into the greenhouse by exposing the resins to the warm moistgreenhouse air.

In greenhouses located in warm in desert climates such as found in theSouthwest United States, the outside CO₂ loading may be performed atnight when outside temperatures are cooler which may enhance CO₂ uptakecapacity. In cooler climates where greenhouses rely in part on radiativeheating, our system of CO₂ loading avoids the need to let in cold air toreplenish the CO₂ and thus reduces the need for heating employing fossilfuel consumption until temperatures drop so low that fuel based heatingbecomes necessary.

In one embodiment, we employ several filters made from humiditysensitive ion exchange active material. In one part of the cycle thefilters are exposed to outside air that could be driven by natural windflow, by thermal convection, or fans. It is preferable to avoid fans asthey add an unnecessary energy penalty. In a second part of the cycle,moist air from inside the greenhouse preferably is driven through thefilter material, e.g. by fans, which then releases CO₂ into thegreenhouse atmosphere. Since the climate control of the greenhousetypically will rely on a fan system anyway, there is little or no energypenalty.

Since plants at night respire, in some greenhouse designs it is possibleto strip the CO₂ from the greenhouse air by pulling the greenhouse airthrough the filters. The filters can then be exposed to higher humidityto facilitate the daytime release of the CO₂ into the greenhouse.

In one embodiment, as shown in FIGS. 2A and 2B, the filter units 10 arelocated adjacent an exterior wall 12 of a greenhouse, and outside air orgreenhouse air routed selectively therethrough, as the case may be, viapivotally mounted wall panels 14. Alternatively, as shown in FIGS. 3Aand 3B, the filter material 10 may be located exterior to and adjacentthe roof 18 of the greenhouse, and outside air or greenhouse air routedselectively therethrough, as the case may be, via pivotally mounted roofpanels 20.

In yet another embodiment of the invention, shown in FIG. 4, the filterunits 10, can be moved from outside the greenhouse where they extractCO₂ from the air to inside the greenhouse where they release thecaptured CO₂. One possible option for doing this is to have filter unitsmounted to pivotally mounted wall or roof panels 22 which can bereversed so that a filter unit on the outside of the greenhouse isexposed to the inside of the greenhouse and vice versa. Filter unitsthat are inside the greenhouse can have air blown through them by a fansystem. Filter units on the outside are exposed to ambient air. In apreferred embodiment, shown in FIG. 4, the filter units 10 on theoutside are located adjacent the bottom end of a convection tower 24that is solar driven. Preferably the inlets are installed at the bottomend of the convection towers where cool air enters and flows up thetowers through natural convection.

In yet another embodiment, shown in FIG. 5, the filter units 10 aremoved in and out of the greenhouse, e.g. suspended from a track 26.

Referring to FIG. 6, yet another option for a greenhouse is to locateconvection towers as double glass walls on the outside of thegreenhouse, and use the convection stream generated to collect CO₂ onthe outside. The double walls also serve to reduce the heatload on theinterior during the day and thus reduce the need for air exchange whichin turn makes it possible to maintain an elevated level of CO₂ in thegreenhouse. The double glass walls also reduce heat loss during thenight.

In this example a protective glass surface 40 may be provided to keepsome of the heat away from the main roof of the glass house 42, causinga convective flow 44 of ambient air over the roof surface. The flow ofambient air is passed through a CO₂ absorbing filter medium 46, whichcan by some mechanism, such as a rotating roof panel 48, exchange placeswith a second like filter medium 50, where the air driven by fan 52 onthe inside of the greenhouse is passed through the filter medium whichgives up the CO₂ captured when the filter medium was exposed to ambientair outside the greenhouse. Because the air inside the greenhouse ismoist, the CO₂ readily is released from the filter medium, and adds tothe CO₂ available in the greenhouse.

An advantage of such a unit is that it could operate at elevated levelsof CO₂ without combusting fuels. Because CO₂ is delivered to the insideof the greenhouse without blowing air into the greenhouse, this offers apossibility of reducing the exchange of air between the outside and theinside of the greenhouse, thus improving the heat management andmoisture management of the greenhouse.

In a second exemplary embodiment of the invention, the CO₂ is extractedand delivered to an algal or bacterial bioreactor. This may beaccomplished using conventional CO₂ extraction methods or by using animproved extraction method as disclosed in our aforesaid PCTapplications or disclosed herein; e.g., by a humidity swing. A humidityswing is advantageous for extraction of CO₂ for delivery to algaebecause the physical separation allows the use of any collector mediumwithout concern about compatibility between the medium and the algaeculture solution. Transfer of gaseous CO₂ allows for the selection ofany algae species, including macro and microalgae, marine or freshwateralgae. Therefore, the selection of algae species to be grown could besolely dependent on environmental factors and water quality at thecollector site. For example, the algae species to be used could beselected from algae naturally occurring at the site, which are uniquelyadapted to the local atmospheric, environmental and water qualityconditions.

There are two major advantages of transferring captured CO₂ in gaseousform. The first advantage is that the collector medium and/or thecollector regeneration solution will not contact the algae culturesolution and/or algae. The second is that all species of algae arecapable of absorbing gaseous CO₂.

Depending on the CO₂ tolerance of particular algae cultures, theCO₂-enriched air can be pumped successively through several algaecultures in order of decreasing CO₂ tolerance and increasing CO₂ uptakeefficiency. Alternatively the air can be diluted to the optimum CO₂concentration.

Referring to FIG. 7, one embodiment of the present invention takesadvantage of the fact that gaseous CO₂ can be driven off the collectormedium using a humidity swing. The humidity swing will transfer capturedCO₂ as gaseous CO₂ from the collector 110 into the algae culture 116. Anion-exchange collector medium loaded with CO₂ will emit gaseous CO₂ whensubjected to an increase in humidity or when wetted with water. And thecollector medium will absorb more gaseous CO₂ when the humidity of theCO₂-supplying gas stream is decreased and/or the collector medium dries.

The present invention provides a common headspace above the collectormedium and the algae culture. This exposes the algae to gaseous CO₂while physically separating the collector medium from the algae culturesolution. The headspace will be sealed from ambient air. The humidity isthen raised in the closed headspace volume. Alternatively, the collectormedium may be wetted. The CO₂ emitted from the collector medium quicklydiffuses through the entire headspace and contacts the algae culturesolution surface.

The CO₂ is then transferred into the algae culture either via gasdiffusion or by bubbling the headspace gas through the algae culturesolution using a recirculating pump. As the algae removes the CO₂ fromthe headspace, the collector medium continues to offgas untilequilibrium is reached. The algae culture solution can be mechanicallystirred. All other nutrients and light are provided to the algae asneeded. The algae may then be collected in an algae harvester 120.

CO₂ concentrations in the headspace above wetted collector medium are upto 20%; or 0.2 atmosphere partial pressure. The concentration can beregulated by the volume to volume ratio of collector medium toheadspace. Also the collector medium can release 60% of the captured CO₂during a humidity swing/wetting.

Alternatively, it is also possible to pump gas from the collector mediumvolume through the algae culture in order to transfer the CO₂. If thealgae pond is warm and moist the moisture from the algae pond may besufficient to stimulate the release of CO₂ from the dry resin, again bythe humidity swing mechanism.

Referring to FIG. 8, in another embodiment of the present invention CO₂concentrations in ambient air can saturate the ion-exchange medium withCO₂ to the level that the CO₂ is bound as bicarbonate anion. Thisembodiment provides regeneration of the collector medium using analkaline solution. During the regeneration, the anion composition in thesolution is changed to approximately 100% bicarbonate. Aqueousbicarbonate solution is not stable under atmospheric conditions andreleases gaseous CO₂. Gaseous CO₂ emission can be enhanced by bubblingthe headspace air through the solution using a recirculating pump.

An alternative embodiment provides a common headspace above thecollector regeneration solution and the algae culture solution. Thisexposes the algae to gaseous CO₂, while separating the regenerationsolution from the algae culture solution. In other aspects, thisheadspace operates similar to the headspace for the collector medium, asdiscussed above.

Referring to FIG. 9, another alternative embodiment of the presentinvention uses an electrodialysis (ED) process to free gaseous CO₂ fromthe loaded collector solution. The freed CO₂ is then transferred into analgae culture 216. The transfer of gaseous CO₂ from the collector 210 tothe algae culture 216 through an electrodialysis (ED) process has theadvantage that the collector solution or sorbent and algae culturesolution are physically separated from each other at all stages of theprocess. This prevents the mixing of the two solutions and also preventsion exchange between the solutions. The ED process has this in commonwith the humidity swing process. And as in the humidity process, thephysical separation allows the use of any collector medium and any algaewithout regard to compatibility between the medium and the algae culturesolution.

An alternative embodiment of the invention takes advantage of the factthat gaseous CO₂ can be driven off the collector regeneration solutionusing an ED process. In the ED process the loaded collector regenerationsolution is split into two streams to enter the ED cell 214. Protons areadded to the first stream across a secondary membrane 236 and theinorganic carbon is driven off as gaseous CO₂, while the sodium cationsare transferred through a cationic membrane 234 into the second stream.In addition to the sodium ions, hydroxide ions are added to the secondstream across another secondary membrane 236 thus neutralizing thebicarbonate in this stream to carbonate.

The first stream exits the ED cell as water or dilute sodium bicarbonatesolution while the second stream exits as a concentrated sodiumcarbonate solution. The two streams are combined to form fresh collectorsolution. The gaseous CO₂ that is driven off the first stream is bubbledinto the algae culture and is fixated as biomass.

As inorganic carbon is removed from the brine, the solution turns morealkaline and additional bicarbonate needs to be added to maintain thepH. Filtration allows us to recover some of the fluid and thus returnwater and sodium from the bioreactor. In one particular implementationthe electrochemical cell will run between two separate fluid cycles, onefairly alkaline which runs between the collector and the base side ofthe electrochemical cell, and the other which runs at near neutral pHbetween the algae-reactor and the acidic side of the cell. Carbonic acidis transferred from the base side to the acid side of the cell. Thisstep regenerates the wash and reloads the fluid with CO₂.

By feeding the bicarbonate sorbent to the algae, CO₂ can be removed fromthe sorbent without first converting the CO₂ back to CO₂ gas. Moreover,by selection of suitable sorbent material for the air capture side, thepH of the washing fluid can be kept relatively low, and if one usesalgae that can tolerate a relatively high pH, the pH difference thatneeds to be made up by electrodialysis becomes relatively small, and insome implementations one can completely eliminate the dialysis cell.

Referring to FIG. 10, another embodiment of the present invention usesan ED process to decrease the bicarbonate concentration in the collectorsolution and to increase the bicarbonate concentration in the algaeculture solution. The collector solution enters the ED cell 214 in thebicarbonate state, while the algae culture solution enters the ED cellin the carbonate state. When the fluids exit the ED cell, the collectorsolution is in the carbonate state and the algae culture solution is inthe bicarbonate state.

Since cations are transferred from the algae culture solution to thecollector solution, the algae culture solution is diluted to roughlyhalf its normality, while the collector solution roughly doubles itsnormality. To make up for the sodium imbalance, half of the loadedcollector solution (bicarbonate form) is transferred directly from thecollector to the algae culture.

In a process scheme according to the present invention, cations aretransferred from the algae solution into the collector solution througha cation exchange membrane 234. The algae culture solution containspredominantly sodium cations, but also potassium, magnesium and calciumions as well as traces of other metal cations. The potential transfer ofmagnesium and calcium is of concern, since both ions form fairlyinsoluble carbonates and hydroxides. The formation of these salts, alsoknown as scaling, can foul up the membranes in the ED cell and/or thecollector medium.

Calcium and magnesium are added to the algae culture as mineralnutrients, at the start of an algae growing cycle. As the algae biomassincreases calcium and magnesium are taken up into the biomass and theirconcentration in the algae culture solution decreases. Simultaneously,the culture solution pH increases as the bicarbonate solution is changedinto a carbonate solution. If magnesium, calcium and carbonate ions arepresent above their solubility products, chemical precipitation willfurther decrease the magnesium and calcium ion concentrations.

The exhausted culture solution with decreased calcium and magnesiumconcentrations and a high pH is entered into the ED cell. There theculture solution is changed from a carbonate into a bicarbonate solutionand its pH decreases accordingly. As the carbonate ion concentrationdecreases, the solution can hold more calcium and magnesium. So scalingis unlikely to happen in this part of the ED cell.

However, at the same time, cations including calcium and magnesium aretransferred from the algae culture solution 216 to the collectorsolution half-cell of the ED. In this half-cell, the bicarbonatesolution coming from the collector is changed into a carbonate solution:the carbonate concentration and the pH increase. Further, excess H₂O maybe removed from the bicarbonate solution using an osmosis cell 224.

The process is designed such that the pH of the exiting collectorsolution is close to the pH of the incoming algae solution. Therefore,scaling should not occur as long as everything is in balance. However,to keep perfect balance may not always be practical on the macro scale,and it may be impossible on the micro scale within the ED cell. It ispossible that micro layers or pockets with increased hydroxide or cationconcentrations are formed at the membrane surfaces. Increasedconcentrations at the surface of the membranes might cause scaling inthe collector solution half-cell.

To minimize scaling, the flux of calcium and magnesium cations has to beminimized. This is a problem well known in the manufacture of salt fromseawater, sodium hydroxide manufacture, and in processing of skim milkby electro dialysis (T. Sata, 1972; T. Sata et al., 1979, 2001; 3.Balster, 2006). To minimize flux, the cationic membrane that separatesthe two half-cells has to be monovalent ion selective. In general,strong acid cation exchange membranes show larger transport numbers fordivalent than monovalent ions. It is assumed that this is due to higherelectrostatic attraction with the negatively charged fixed ion exchangesites. The prior art has shown that transport numbers for divalentcations decrease with lower charge density on membranes.

Two commercially available highly monovalent cation selective membraneshave been identified as particularly suited for this process. Onemembrane is manufactured by Asahi Glass and is traded under the nameSelemion CSV. The second is manufactured by Tokuyama Soda and is soldunder the name Neosepta® CIMS. The transport numbers (t) for SelemionCSV are: t(Na)<0.92 and t(Ca,Mg)<0.04. The transport numbers forNeosepta CIMS are t(Na,K)=0.90 and t(Ca,Mg)=0.10. The transport numbersare defined as the equivalence flux of the cation divided by the totalequivalence flux during electrodialysis.

This aspect of the invention uses a monovalent cation selective membraneto minimize the transfer of multivalent cations from the algae culturesolution into the collector regeneration solution. Any scaling built upwith time, will be removed using an acid solution.

Both the algae culture solution as well as the collector solution willbe filtered before entering the ED cell to avoid membrane fouling withparticles. Organic molecules will be scavenged from the algae culturesolution by means of organic scavenging ion exchange resins.

Referring to FIG. 11, in another embodiment of the present invention theCO₂ captured from air is transferred to the algae by feeding the loadedcollector solution 310 to the algae. The loaded collector solution isenriched in sodium bicarbonate. Nutrients are added to the collectorsolution and it becomes the feed stock for algae. In this embodiment ofthe invention the solution feed is not recycled, so that the collectorsolution becomes a consumable.

In this process the algae culture solution 316 would increase in saltcontent as more and more sodium bicarbonate is added. The sodiumbicarbonate is changed into carbonate during algae growth. To lower thecarbonate concentration and to slow the salting, some of the remainingnutrients can be added as acids instead as sodium salts, which willconvert carbonate ions to bicarbonate and minimize the addition ofsodium.

Alternatively, the sodium bicarbonate sorbent is fed directly to analgae-reactor to supply the algae with CO₂, and the algae is removed forfurther processing, with the sodium carbonate being returned to the airextraction station.

Many algae can utilize bicarbonate as their carbon source. Also, somealgae prefer bicarbonate over CO₂ as their carbon source. These areoften algae that are indigenous to alkaline lakes, where inorganiccarbon is predominantly present as bicarbonate. These algae can toleratelarge swings in pH of 8.5 up to 11. Other algae can utilize HCO₃ ⁻ astheir carbon source, but require pH ranges below pH=9, which wouldrequire bubbling CO₂ through the bicarbonate/carbonate solution.

Algae use the carbon source to produce biomass through photosynthesis.Since photosynthesis requires CO₂ not bicarbonate, the algae catalyzethe following reaction:

HCO₃ ⁻→CO₂+OH⁻

In the presence of HCO₃ ⁻, this becomes:

HCO₃ ⁻+OH⁻→CO₃ ⁻²+H₂O

Algae growth in a bicarbonate solution induces the following changes inthe solution: (1) a decrease in HCO₃ ⁻ concentration; (2) an increase inCO₃ ⁻² concentration; and (3) an increase in pH.

Another embodiment the present invention uses an algae culture solutionfor collector regeneration. The collector medium in the carbonate formcan absorb gaseous CO₂ from ambient air until the anion composition ofthe medium is nearly 100% bicarbonate. In this state the collectormedium is fully loaded and CO₂ absorption comes to a halt. A carbonatesolution can be used in regeneration to return the loaded collectormedium to a carbonate form through ion exchange. The anion compositionof the regeneration solution can be changed from 100% carbonate tonearly 100% bicarbonate through anion exchange with the fully loadedcollector medium. In a counter-flow regeneration process the collectormedium can be brought into a carbonate form, while the carbonateregeneration solution is changed into a bicarbonate solution. Theregeneration solution is fully loaded when it is in the bicarbonateform, since it cannot remove any more bicarbonate from the collectormedium.

The algae are introduced into the process to remove the captured CO₂from the loaded regeneration solution by bicarbonate dehydration andneutralization (see above). The algae utilize the freed CO₂ for biomassgrowth. And the regeneration solution is changed from bicarbonate backinto a carbonate solution.

In this process, the carbonate regeneration solution and the collectormedium are recycled, while ambient air CO₂ is changed into algalbiomass. This is shown in FIG. 11.

This process provides a cycle in which the ion exchange collector mediumabsorbs air CO₂. During the absorption the collector medium changes fromcarbonate to bicarbonate form. Then the regeneration solution pulls theair CO₂ from the loaded collector medium. In this exchange the collectormedium is changed back into its carbonate form, while the regenerationsolution changes from a carbonate to a bicarbonate solution. Finally,the algae remove the air CO₂ from the loaded regeneration solution byfixating it into biomass. In this step, the algae catalyze the reactionfrom bicarbonate to CO₂ and carbonate. The CO₂ carbon is bound into thealgae biomass. The carbonate is left in solution. The resultingregeneration solution is then in carbonate form.

In another embodiment of the present invention, the algae culturesolution is used as the collector regeneration solution. This means thatthe collector regeneration solution will in addition to carbonatecontain other nutrients as required for the algae. Amongst thesenutrients are anions that will compete with the carbonate anion duringion exchange with the collector medium.

In this process diatoms will not be used, since they require silica,which cannot be efficiently removed from the collector medium with acarbonate wash.

Other anionic nutrients typically found in algae culture mediums are:nitrate (NO₃ ⁻), sulfate (SO₄ ⁻²), and phosphate (PO₄ ⁻³). Phosphorusmay also be present as dibasic (HPO₄ ⁻) or monobasic phosphate (H₂PO₄ ⁻)depending on pH.

Nitrate, sulfate and phosphate concentrations for typical algae culturemediums are:

Bold's Medium Zarouk's Medium Nutrient Molarity (M) Molarity (M) NaHCO₃0.2 NaNO₃ 0.00882 0.029 Mg SO₄—7H₂O 0.0003 0.0008 Fe SO₄—7H₂O 0.0018K₂SO₄ 0.0058 Total S Σ = 0.0003 Σ = 0.0084 K₂HPO₄ 0.00043 0.0029 KH₂PO₄0.00129 Total P Σ = 0.00172 Σ = 0.0029

However, the prior art has shown that algae can grow at much lowernutrient concentrations than are contained in typical culture mediums.

To estimate the effect of the nutrient concentrations on the collectormedium a nutrient-containing regeneration solution was mixed as follows:0.14 M CO₃ ⁻², 0.04 M NO₃ ⁻, 0.0017 M SO₄ ⁻² and 0.0017 M H₂PO₄ ⁻. Theserepresent the highest concentrations to be found in an algae culturemedium and, therefore the worst-case scenario.

The collector medium was then flushed with this ‘worst-ease’ solutionuntil equilibrium was reached between the solution and the collectormedium. At the pH of carbonate solution, phosphorus is present asdibasic phosphate (HPO₄ ⁻²). Dibasic phosphate is basic enough to absorbCO₂. Therefore, the presence of dibasic phosphate anions on thecollector medium will not lower the medium's CO₂ uptake capacity. It wasdetermined that at equilibrium, about 50% of the collector medium'stotal exchange sites were occupied by carbonate and phosphate ions and50% by nitrate and sulfate. Although the other nutrients outnumbercarbonate, they do not completely replace it; instead, an anionequilibrium is reached that does not change with application ofadditional volumes of solution to the collector medium.

The experiments showed that in a worst-case scenario, the collectormedium looses approximately 50% of its CO₂ uptake capacity. However, asdetermined by the research cited above, the nutrient concentrations inthe solution can be depleted significantly during algae growth. Forexample, nitrate being by far the most abundant nutrient after inorganiccarbon, can be reduced to 0.002 M, a mere 5% of the concentration usedin the worst-case scenario experiment. And phosphate is reduced to 45%of the worst-case scenario.

Further, a collector medium washed with a nutrient-depleted solutionwill loose about 20% of its CO₂-uptake capacity. It is thereforepossible to use the collector medium and wash it with a carbonatesolution that has been derived from the algae growth medium.

The algae will secrete or release organic compounds into the solutionduring metabolism or decay. These organics will be scavenged from thesolution, prior to applying the solution to the collector medium.Organics scavenging may be done with an adsorbent-type ion exchangeresin or other processes.

Diatoms will not be used in this process, since they require silica,which cannot be efficiently removed from the collector medium using acarbonate wash.

A preferred algae for the present embodiment will have the followingcharacteristics: they are adapted to high ionic strength liquids; theycan grow in a pH range of 8.5 to roughly 11; they can tolerate a gradualpH change; they can use bicarbonate as their carbon source; they needlittle silica as a nutrient; they are capable of changing the pH of asolution from 8.5 to 11 or above; they can diminish nutrientconcentrations to low levels; they can be used in biochemistry,agriculture, aquaculture, food, biofuels, etc.

Good candidates are, but are not limited to, algae that live in alkalinewaters such as Spirulina platensis, Spirulina fusiformis, Spirulina sp.,Tetraedron minimum and others.

There are many alternatives for this embodiment. Loaded collectorsolution (bicarbonate solution depleted in nutrients) is added to analgae culture together with fresh nutrients; the algal culture utilizesbicarbonate as its inorganic carbon source, by taking up about 50% ofthe bicarbonate carbon into its biomass and changing the remaining 50%to carbonate anions. Simultaneously, the algae culture depletes thenutrient concentrations in the solution. The culture is filtered,harvesting the algae biomass, while shunting the nutrient depletedsolution towards the CO₂ collector. The nutrient depleted solution iscleaned of organics and other materials deleterious to the collectormedium. The solution now enriched in carbonate is used to regenerate thecollector. In the process each carbonate anion is replaced by twobicarbonate anions, until the collector solution is loaded. The loadedcollector solution is added to the algae culture together with freshnutrients as mentioned above.

The process can be run as a continuous loop or a batch process,whichever is more practical given location, algae type, etc. The processcan employ algae culturing technologies already in use and proven or newtechnologies. For example, outdoor ponds have proven successful for thecultivation of Spirulina, Chlorella vulgaris, Ankistrodesmus braunii andother species in California, Hawaii, the Philippines and Mexico amongother places. According to the National Renewable Energy Laboratory(NREL), outdoor ponds, e.g. so-called “race ponds”, are the mostefficient methods for growing a large biomass of algae.

The cultivation may use solar energy, artificial lighting or bothdependent on the algae species and the place of operation. Algae culturesolutions may be stirred to return algae to the zone of highest lightingress. Or the light might be brought into the algae cultures throughmirrors, fiber optics and other means.

The algae can be either suspended in solution or immobilized. Whensuspended, algae follow their own growth patterns: single cells,colonies, clumped and so on. The natural growth pattern may not be thebest match for the technology used. For example, small single celledalgae may require elaborate harvesting processes.

Algae may naturally grow immobilized, if they attach themselves tosurfaces, e.g., macro algae. Or algae can be immobilized: in beads usingk-carragenan or sodium alginate, in polyurethane foam, on filtermaterial, or as biofilms on column packing, or in other ways.

In an immobilized state, the algae may still be suspended, for examplein bead form, and moving with the solution. Alternatively, theimmobilized algae may be stationary in a column or other device, whilethe solution percolates past.

In another embodiment of the present invention, the collector medium isimmersed into the Algae Culture. This can be done either in a batchprocess or in a continuous process. In a batch process, a batch ofcollector medium is alternatingly immersed in the algae culture andexposed to ambient air. In a continuous process, collector medium iscontinuously moved along a path on which it is alternatingly immersed inthe algae culture or in exposed to air. The easiest implementation wouldbe a disk of collector medium that rotates continuously around itscenter. The disk is submerged up to its center point in the algaeculture, so that, at any time, one half of the collector medium issubmerged in the liquid and the other half is exposed to air.

In this embodiment of the invention, collector medium could potentiallybe immersed in the algae culture solution at times of high nutrientcontent and at times of low nutrient content. The CO₂ capacity of thecollector medium will, therefore, range from 50% to 80% of its fullcapacity. Air exposure times can be adjusted to account for the capacitydecrease.

Referring to FIG. 12, another embodiment of the present inventiondiscloses sodium bicarbonate transferred from the collector solution tothe algae by washing the algae in the loaded collector solution.However, nutrients will not be added to the collector solution. Instead,nutrients will be provided to the algae via a second separate wash cycleconsisting of nutrient-rich carbon deficient solution.

In this process the algae will be immersed in nutrient-deficientbicarbonate solution (loaded collector solution) alternating withinorganic carbon-deficient nutrient solution 326. A short rinse cyclewill be employed between washes. The rinse will be added to the solutionof the preceding wash.

The cycles of nutrient and bicarbonate washes will be optimized for thealgae species used. One or more algae species may be used either mixedor in series to optimize the conversion of the bicarbonate solution(loaded collector solution) to carbonate solution (fresh collectorsolution). The fresh collector solution may be filtered to removeparticles and cleaned of organic molecules or other deleterious contentprior to application on the collector medium.

The process can be designed to utilize suspended algae or immobilizedalgae. If the algae are suspended, the process has to be run as a batchprocess, and the algae have to be filtered from the solution. To easefiltering the algae may be “immobilized” in suspended beads, in order toincrease the particle size.

A process involving immobilized algae can utilize algae that naturallygrow immobilized, for example macro-algae that attach themselves tosurfaces, or micro-algae that form biofilms etc.

In addition to others methods disclosed elsewhere in this application,the algae could be immobilized in columns, inclined raceways, ponds orother containers. The containers may be arranged to allow gravitationalfluid flow. Immobilization may be on the container walls and floorsand/or on structures such as plates, packing etc. installed therein.Light is brought into the containers as needed either by naturallighting, artificial lighting, mirrors, fiber optics, etc.

Referring to FIG. 13, another embodiment of the present inventiontransfers gaseous CO₂ from the loaded collector solution 410 to thealgae culture solution 416 through a hydrophobic microporous membrane434. Gaseous CO₂ can be transmitted from a bicarbonate solution througha hydrophobic membrane into a carbonate solution; and that the CO2partial pressure differential between the two liquid streams issufficient to drive the transfer. A transfer of water was noted from themore dilute solution to the more concentrated solution. As the membraneis hydrophobic, the transfer is of gaseous water molecules.

Simplified, the process can be described as two half-cells separated bya microporous, hydrophobic membrane. The first half cell 438 holds theloaded collector solution (sodium bicarbonate solution); while thesecond half cell 418 holds the algae culture (sodium carbonate solutionincluding nutrients and algae).

The collector solution half-cell reaction is defined as follows:

2HCO₃— (aq)→CO₂ (g)+CO₃ ⁻² (aq)+H₂O

This is followed by CO₂ (g) diffusion through membrane into the algaeculture half-cell. The reaction in the algae culture half-cell willfollow in one of two ways:

-   -   Algae consume CO₂ (g)        -   or

CO₃ ⁻² (aq)+CO₂ (g) H₂O→2HCO₃— (aq)

and

HCO₃ ⁻ (aq)+OH⁻→CO₃ ⁻² (aq)+H₂O

As can be seen from the half-cell reactions, the pH in the collectorsolution will continuously increase as bicarbonate is reacted intocarbonate through off-gassing of gaseous CO₂. In a balanced system thealgae culture solution will not change its pH as the gaseous CO₂ isfixated by algae growth into biomass. The algae culture will preferablybe close to a carbonate solution. In that case, it would not containappreciable amounts of bicarbonate. This condition would maximize thegaseous CO₂ partial pressure differential between the collector solutionand the algae culture.

The physical arrangement of the two half-cells can take many formsincluding but not limited to the few arrangements described herein. Eacharrangement will optimize the ratio of liquid-membrane contact area tosolution volume. In general it is advantageous to run the collectorsolution through membrane channels submerged in the algae culture, sincethis will enable light supply to the algae culture. In cases where thealgae culture is contained in membrane conduits, light will be suppliedinside the conduits.

The membrane conduits can take many shapes. For example, they can beparallel membrane sheets, causing a sheet flow of solution sandwichedbetween the membranes. Or they could be tubular with the tubecross-section taking varying forms, for example round, square,rectangular, corrugated, etc. Tubes could form a spiral or other shapesto increase their path length through the solution.

The process can be run as a batch procedure, a continuous loop processor any combination thereof. Light and nutrients will be supplied asneeded.

In a pure batch process, a batch of loaded collector solution is broughtin membrane contact with a batch of algae culture and left to reachequilibrium.

In a pure continuous loop process both solutions flow in continuousloops. The loaded collector solution would flow along a membrane path,throughout which it transfers its gaseous CO₂ to the algae solution;from there it enters the regeneration system for the collector medium,where it loads up with CO₂ to then reenter the membrane conduit. Thealgae solution will flow past the membrane path with algae fixating thegaseous CO₂; from there it will enter a harvesting system 420, wheresome or all algae are removed from the solution to then reenter themembrane system for renewed CO₂ fixation and algae growth. Continuousflow or loop processes may use concurrent flow or counter-current flowof the two streams.

The major advantage of transferring the CO₂ through a hydrophobicmembrane is that ions cannot cross from the algae culture into thecollector solution. The cations contained in the algae solution includeearth alkali metals that can cause scaling along the collector solutionpath as the pH increases. The anions, such as nitrate and sulfate,contained in the algae solution compete with carbonate on the collectormedium thus lowering the CO₂ holding capacity of the collector medium.Therefore, it is advantageous to keep the ions from entering thecollector solution. Since ions, which constitute the nutrients for thealgae, cannot cross into the collector solution, the nutrient content ofthe algae culture can be permanently kept at the optimum concentrationfor algae growth.

In addition, the prior art discloses hydrophobic membranes that are alsoorganophobic and can impede the transfer of organic molecules from thealgae solution to the collector solution. Any organics that may betransferred into the collector solution will be removed from thecollector solution before it enters the collector medium. For example,this can be done by scavenging the organic compounds onto ion exchangeresins.

The membrane will be selected for its hydrophobicity, CO₂ permeability,organophobicity, and water break-through pressure. The preferred algaefor this process are those that thrive in carbonate solutions and canboth utilize gaseous CO₂ and bicarbonate. However, other algae can alsobe used to optimize the complete process.

Referring to FIG. 14, another embodiment of the present inventiontransfers bicarbonate from the collector solution 410 into the algaeculture solution 418 through an anion permeable membrane. The collectorsolution is brought into contact with one side of the anion permeablemembrane 434, while the algae culture solution is brought into contactwith the other side of the membrane.

The solutions exchange anions along concentration gradients. To optimizethis ion exchange, the solutions can be run past the membrane in acounter-current. The solutions can also be run co-current to optimizeother parts of the system. Alternatively, the process can be set up as abatch process rather than a continuous flow process.

The algae culture solution can be entered into the anion exchangeprocess with algae suspended in the solution or without the algae. SeeFIG. 15. Dissolved organic compounds can be removed from the algaeculture solution prior to entering the membrane chamber.

Nutrient effects apply as discussed above. If the whole algae cultureincluding algae is entered into the membrane exchanger, the nutrientconcentration will be high and the collector solution will gain highnutrient concentrations. This may lead to a reduction in the collectormedium's CO₂ uptake capacity of up to 50%. If the culture solutionwithout algae is entered into the membrane exchanger, the process can beset up such that nutrient-depleted solution is entered, in which casethe collector capacity might be reduced by up to 20%.

Cations will not be exchanged between the two solutions, which greatlyreduces the potential for scaling.

Alternatively, one can inject captured CO₂ directly into analgae-bio-reactor synthetic fuel production unit. A particularly simpledesign is to provide a paddle wheel or disks or the like carryinghumidity sensitive ion exchange resins that are exposed primarily abovethe water surface where CO₂ is extracted from the air, and are slowlyrotated to dip a portion under the water surface where the CO₂ isreleased to provide high air-to-water transfer rates for the CO₂.

Referring to FIG. 16, in another embodiment it is possible to shower anion exchange resin with slightly alkaline wash water at an extractionstation 140, similar to the first exemplary embodiment, to make upevaporative or production losses of water from the bioreactor. As thewash water trickles over the primary resin, it will pick up bound CO₂and dribble it into the bioreactor system 142.

Alternatively, as shown in FIG. 17, resins 142 may be added to the waterat night to retain the CO₂ that may be lost from the algae due torespiration. Thus we can improve the CO₂ uptake efficiency of the algae,by preventing the release of nighttime CO₂ from the bioreactor. In suchembodiment, a secondary resin acts as a carbon buffer in the system. Atnight this buffer stores the CO₂ released by the algae, while during theday it provides CO₂ to the algae, while its CO₂ content may besupplemented by the CO₂ that is collected by the air collector. Oncecaptured, the CO₂ is transferred to the resin from a more concentratedwash used in regenerating the primary resin. Water filtration to keepalgae out of the air collector generally is not a problem due to thefact that the air-side primary resin is designed to completely dry outin between cycles.

This transfer to the secondary resin also could be accomplished withoutdirect contact in a low-pressure closed moist system, such as shown inFIG. 1, by performing a humidity swing that avoids direct contact withthe water. While such a system loses the aforementioned advantage of notbringing CO₂ back to the gas phase, it will have other advantages inbuffering the algae pond at a constant pH, without the use of chemicals.

In a preferred embodiment of the invention, as seen in FIG. 18, in orderto reduce water losses, increase yield, and better confine the algae, weemploy bioreactors 150 with light concentrators 152. Such systems may bebuilt from glass tubes surrounded by mirrors, or mirror or reflectorsystems that feed into fiber optic light pipes that distribute the lightthroughout a large liquid volume. The advantage of the use of abioreactor with light concentrators is that they greatly reduce thewater surface and thus reduce water losses.

Thus, the CO₂, can be collected nearby without directly interfering withthe algae reactors. Indeed air collectors could take advantage of mirrorsystems for guiding air flows.

Algae typically fixate CO₂ during times of light influx, and respire CO₂during dark cycles. The CO₂ is captured by adding additional collectormedium to the system in strategic places. The collector medium can, forexample, be immersed in the algae culture. In this case, it will storebicarbonate and release carbonate during respiration as the culturesolution pH decreases, and it will release bicarbonate and storecarbonate during photosynthesis as the culture solution increases in pH.

Collector medium can also be placed in the air space in proximity of thealgae culture to absorb CO₂ that has been released from the culturesolution. This will be especially efficient in closed structures.Collector medium placed in the proximity of the culture solution will beregenerated using one of the processes described above.

This application is intended to include any combination of the inorganiccarbon transfer methods described in this patent using any combinationof algae cultures as required to optimize the process. Optimizationincludes but is not limited to optimization of the carbon transferefficiency, carbon transfer rate, market value of the biomass (forexample oil content, starch content etc.), algae productivityefficiency, and algae growth rate under any climate conditions orclimate-controlled conditions.

While the invention has been described in connection with a preferredembodiment employing a humidity sensitive ion exchange resin materialfor extracting CO₂ from ambient air and delivering the extracted CO₂ toa greenhouse by humidity swing, advantages with the present inventionmay be realized by extracting carbon dioxide from ambient air using asorbent in accordance with the several schemes described in ouraforesaid PCT Application Nos. PCT/US05/29979 and PCT/US06/029238(Attorney Docket Global 05.02 PCT), and releasing the extracted CO₂ intoa greenhouse by suitably manipulating the sorbent.

1-46. (canceled)
 47. An apparatus for the capture of CO₂ from aircomprising an anion exchange material that captures CO₂ from a flow ofair and from which captured CO₂ is releasable by wetting or a swing inhumidity; a wetting or humidity source; and a sealed enclosure forcontaining CO₂ released from said anion exchange material.
 48. Theapparatus of claim 47, further comprising a pump that bubbles CO₂released from said anion exchange material into an algae culture. 49.The apparatus of claim 47, wherein said anion exchange material iscontinuously cycled between exposure to air and release of captured CO₂.50. The apparatus of claim 47, wherein said anion exchange materialextracts CO₂ when dry and releases CO₂ when exposed to higher humidity.51. The apparatus of claim 47, wherein the anion exchange material is acomponent of a heterogeneous ion exchange material.
 52. The apparatus ofclaim 47, wherein the anion exchange material comprises a strong baseresin.
 53. The apparatus of claim 52, wherein said resin comprises aType 1 or Type 2 functionality ion exchange resin.
 54. The apparatus ofclaim 53, wherein said ion exchange resin comprises Anion I-200 ionexchange membrane material.
 55. The apparatus of claims 47, furthercomprising a sorbent to which released CO₂ is transferred.
 56. Theapparatus of claim 55, wherein said sorbent is selected from the groupconsisting of: liquid amines, ionic liquids, solid CO₂ sorbents, lithiumzirconate, lithium silicate, magnesium hydroxide, and calcium hydroxide.57. The apparatus of claim 55, wherein said sorbent comprises an ionexchange resin.
 58. The apparatus of claim 47, wherein the concentrationof CO₂ in said enclosure is at least 3%.
 59. The apparatus of claim 47,wherein the concentration of CO₂ in said enclosure is between 3% and10%.
 60. The apparatus of claim 47, wherein the concentration of CO₂ insaid enclosure is close to 100%.
 61. The apparatus of claim 47, whereinthe concentration of CO₂ in said enclosure is up to 20%.
 62. Theapparatus of claim 47, wherein said anion exchange material comprises amaterial from which 60% of said captured CO₂ is releasable by wetting orswing in humidity.
 63. The apparatus of claim 47, wherein said sealedenclosure comprises a headspace above an algae culture.
 64. Theapparatus of claim 47, wherein said apparatus is located adjacent to acontrolled environment into which captured CO₂ is released.